JP2000044827A - COMPOSITION FOR DYING KERATIN FIBER INCLUDING PYRAZO[1,5- a]PYRIMIDINES, PROCESS DRYING THE SAME, NEW PYRAZO[1,5- a]PYRIMIDINES AND MANUFACTURE OF THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain pyrazo[1,5-a]pyrimidines useful for an oxidizing base in a medium for oxidizing dye of keratin fibers especially human keratin fibers. SOLUTION: The compound is expressed by formula I R1 to R4 are each H, an 1 to 4C alkyl or the like; X is H, sulfonic acid or the like; i is 0 or 1 to 3; p, q and n are each 0 or 1; however p+q≠0 and n is 0 when p+q=2, NR1R2 and NR3R4 are each in position (2, 3), (5, 6) or the like, and n=1 when p+q=1 and NR1R2 (or NR3R4) and OH are each in position (2, 3), (3, 5) or the like, excluding pyrazo[1,5-a]pyrimidine-6,7-diamine}, for example pyrazo[1,5- a]pyrimidine-3,7-diamine. The compound of formula I is manufactured by cyclizing, for example, 4-nitro-2H-pyrazol-3-ylamine hydrochloride in the presence of derivatives of acrylonitrile of formula III to afford the compound of formula IV and reducing the compound to obtain the compound of formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel composition for oxidative dyeing of keratin fibers, comprising at least one pyrazolo [1,5-a] pyrimidine derivative as an oxidation base, and a dyeing method using the composition. , New pyrazolo [1,
5-a] pyrimidine derivatives and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Generally known as oxidation bases are oxidation dye precursors, especially ortho- or para-phenylenediamines such as diaminopyrazole derivatives, ortho- or para-aminophenols and heterocyclic compounds. It is known to dye keratin fibres, especially human hair, with a dye composition which does.
Oxidative dyeing precursors, or oxidation bases, are colorless or slightly colored compounds, which, when combined with oxidizing substances, can give rise to colored dyeing compounds by the process of oxidative condensation. The shades obtained with these oxidation bases can also be obtained by combining the oxidation bases with couplers or color modifiers (the latter, in particular, meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds). It is also known that it can be varied.

The variety of compounds used with respect to oxidation bases and couplers allows a wide range of colors to be obtained. The so-called "permanent" coloration obtained with these oxidation dyes must also satisfy a number of certain requirements. Thus, it must not have toxic drawbacks, it must be able to give the shade of the desired intensity, and it has no external agents (light, bad weather, washing,
(Permanent waving, sweating, rubbing). Also, the dye must be able to hide gray hair and, at the end, must be as non-selective as possible, i.e., in fact, the sensitivity (damage) differs between its tip and its root Along the entire length of the same keratinous fiber to be obtained, the color difference must be as small as possible. Also, they must have good chemical stability in the formulation. They must have a good toxicological profile.

Use of certain pyrazolo [1,5-a] pyrimidine derivatives which can be substituted at the ₄ , 5 and / or 6 positions by C ₁ -C ₄ alkyl groups as couplers for the oxidative dyeing of keratin fibers. Are especially proposed in German Patent Application No. 4,029,324. The use of certain pyrazolo [1,5-a] pyrimidine-derived bodies from the tetrahydropyrazolo [1,5-a] pyrimidine family as oxidation dye precursors for the oxidation dyeing of keratin fibers has also been described in Germany. Patent application No. 4,133,9
No. 57.

[0005] Applicants have discovered, quite unexpectedly and surprisingly, a new family of pyrazolo [1,5-a] pyrimidine derivatives of formula (I), some of which are novel per se. The derivatives are potentially suitable for use as oxidation dye precursors and, in addition, make it possible to obtain dye compositions which lead to intense coloration, and use external agents (light, bad weather, washing, permanent waving, sweating, Good resistance to abrasion). Finally, these compounds were found to be easily synthesized and chemically stable. They have a good toxicological profile. These findings form the basis of the present invention.

[0006]

Means for Solving the Problems and Embodiments of the Invention
A first subject of the invention is therefore the at least one pyrazolo [1,5-a] pyrimidine derivative of the following formula (I) and / or acid or base as oxidation base in a medium suitable for dyeing Composition for oxidative dyeing of keratin fibers, especially human keratin fibers such as hair, characterized in that they comprise one of the addition salts with and / or one of their tautomeric forms, if a tautomeric equilibrium exists. Things.

[0007]

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Wherein:-R which may be the same or different₁, R_Two, R_ThreeAnd R_Four
Is a hydrogen atom, C₁-C_FourAlkyl group, aryl group, C₁−
C_FourHydroxyalkyl group, C_Two-C_FourPolyhydroxya
Alkyl group, (C₁-C_Four) Alkoxy (C₁-C_Four) Archi
Group, C₁-C_FourAn aminoalkyl group (the amine is acetyl
Or ureido or sulfonyl),
(C₁-C_Four) Alkylamino (C₁-C_Four) Alkyl groups,
Di [(C₁-C_Four) Alkyl] amino (C₁-C_Four) Archi
(The dialkyl is a 5- or 6-membered alicyclic or
Capable of forming a heterocyclic ring) or hydroxy (C
₁-C_Four) Alkylamino (C₁-C_Four) Alkyl group or
Di [hydroxy (C₁-C_Four) Alkyl] amino (C₁−
C_Four) Represents an alkyl group;-groups X which may be the same or different are a hydrogen atom,₁−
C_FourAlkyl group, aryl group, C₁-C_FourHydroxyal
Kill group, C_Two-C_FourPolyhydroxyalkyl group, C ₁-C_Four
An aminoalkyl group, (C₁-C_Four) Alkylamino (C₁
-C_Four) Alkyl group, di [(C₁-C_Four) Alkyl] ami
No (C₁-C_FourA) alkyl group, wherein said dialkyl is 5- or
Capable of forming a 6-membered alicyclic or heterocyclic ring),
Hydroxy (C₁-C_Four) Alkylamino (C₁-C_FourA)
Alkyl group, di [hydroxy (C₁-C_Four) Alkyl] ami
No (C₁-C_Four) Alkyl group, amino group, (C₁-C_FourA)
Alkylamino or di [(C₁-C_Four) Alkyl] ami
Group, halogen atom, carboxylic acid group or sulfonic acid group
I is equal to 0, 1, 2 or 3;-p is equal to 0 or 1;-q is equal to 0 or 1;-n is equal to 0 or 1; Is non-zero;-(ii) if p + q is equal to 2, then n is equal to 0;
NR₁R_TwoAnd NR_ThreeR_FourIs position (2,3);
(5,6); (6,7); (3,5) or (3,7)
(Iii) if p + q is equal to 1, then n is equal to 1
Shiki, group NR₁R_Two(Or NR_ThreeR_Four) And the OH group
(2,3); (5,6); (6,7); (3,5)
Or (3,7)].

If the compounds of the formula I contain an OH group at one of the 2, 5 or 7α positions relative to the nitrogen atom, for example,
The following reaction formula:

[0010]

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There are tautomeric forms represented by In general, the addition salts with acids (oxidation bases and couplers) which can be used in the sense of the dye compositions according to the invention include, in particular, hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates Is selected from Addition salts with bases (oxidized bases and couplers) which can be used in the sense of the dye compositions of the invention are those obtained with sodium hydroxide, potassium hydroxide, aqueous ammonia or amines.

Among the pyrazolo [1,5-a] pyrimidine derivatives of the formula (I) which can be used as oxidation bases in the compositions according to the invention, mention may in particular be made of: Pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2-methylpyrazolo [1,5-a] pyrimidine-
3,7-diamine; -2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; -pyrazolo [1,5-a] pyrimidine-3,5-diamine; -2,7 -Dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; -3-aminopyrazolo [1,5-a] pyrimidine-7
-3-amino-5-methylpyrazolo [1,5-a] pyrimidin-7-ol;-3-aminopyrazolo [1,5-a] pyrimidine-5
-Ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; -3-amino-7- [beta] -hydroxyethylamino-5
-Methylpyrazolo [1,5-a] pyrimidine; -2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; -2-[(3-aminopyrazolo [1,5-a] pyrimidine- 7-yl) (2-hydroxyethyl) amino] ethanol;-2-[(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) (2-hydroxyethyl) amino] ethanol;-5,6- Dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; -2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; -2,5-N-7, N-7-tetramethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; and its addition salts and tautomers in the presence of tautomeric equilibrium.

The pyrazolo [1,5-) of the present invention of the formula (I)
a] Pyrimidine derivatives can be prepared by known methods described in the literature. For example, the following documents can be cited. Pyrazolo [1,5-a] of the invention of the formula (I)
Pyrimidine derivatives can be prepared by cyclization from aminopyrazoles according to the synthetic methods described in the following documents. − EP628559 BEIERSDORF-LIL
LY-R. Vishdu, H. Navedul, Indian J. Chem., 34b
(6), 514, 1995 − NS Ibrahim, KU Sadek, FA Abdel-Al, Arch.
Pharm., 320, 240, 1987 − RH Springer, MB Scholten, DE O'Brien,
T. Novinson, JPMiller, RK Robins, J. Med. C
hem., 25, 235, 1982-T. Novinson, RK Robins, TR Matthews, J.
Med. Chem., 20, 296, 1977-US Pat. No. 3,907,799 ICN PHARMACE.
UTICALS

The pyrazolo [1,5-) of the present invention of the formula (I)
a] Pyrimidine derivatives can be prepared by cyclization from hydrazine according to the synthetic methods described in the following documents. − A. McKillop and RJ Kobilecki, Heterocycles,
6 (9), 1355, 1977 − E. Alcade, J. De Mendoza, JM Marcia-Marquin
a, C. Almera, J. Elguero, J. Heterocyclic Chem. 11
(3), 423, 1974 − K. Saito, I. Hori, M. Higarashi, H. Midorikaw
a, Bull. Chem. Soc., Japan, 47 (2), 476, 1974

The 3-aminopyrazolo [1,5-a] pyrimidine derivative of the formula (I) of the present invention can be prepared, for example, according to the reaction scheme 1
Can be prepared by the process described in

[0016]

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(H. Dorn and H. Dilcher, Liebigs Ann.
Chem. 707, 141, 1967)
2H-pyrazol-3-ylamine hydrochloride (III)
With an acrylonitrile derivative (IV) (Z = MeO, E
tO or Me ₂ N) or acrylate (V) (Z =
Cyclization in the presence of MeO or Me ₂ N; R ′ = C ₁ -C ₄ alkyl, aryl) to give structural formula (VI) (Y = NH
₂ , OH) to pyrazolo [1,5-a] pyrimidine. This reaction is described in Synthesis, 673, 1982.
G. Muhmel, R. Hanke and E. Breitmaier listed in
It is possible to carry out based on the method. 4-nitro-
The list of derivatives that can be cyclized with 2H-pyrazol-3-ylamine (III) is not limited to acrylonitrile and acrylate derivatives only.
For example, the β-ketoester derivative (VIII) (X has the same definition as the group X in the formula (I); R ′ = C ₁ -C ₄ alkyl, aryl), the β-ketonitrile derivative (IX) (X Is a group X in the formula (I)
Or the β-cyanoacetal derivative (X) (R ′ = C ₁ -C ₄ alkyl), but is not limited thereto.

[0018]

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Next, a known method (R. Hemmer, W. Lurk)
en, in Houben-Weyl, `` Methoden der Organischen Chem
ie ", vol. E16d, pp. 815 ff. ), The pyrazolo [1,5-a] pyrimidine of the structural formula (VI) can be reduced. Preference is given to using metals such as palladium (Pd), platinum (Pt) or nickel (Ni) in the presence of a hydrogen donor such as ammonium formate, formic acid or alternatively cyclohexene instead of hydrogen (S. Ram, RE Ehrenkaufer, Synthesis, 91, 198
8). If desired, an organic solvent such as methanol, ethanol or tetrahydrofuran may be added. Zinc (ZZ) in an acidic medium such as aqueous hydrochloric acid or acetic acid may be added.
Metals such as n), tin (Sn) or iron (Fe) can also be used. Preferably, the pyrazolo [1,5-a] pyrimidine derivative of the formula (I) is used in an amount of about 0.0005 to 12% by weight, based on the total weight of the dye composition.
More preferably, it represents approximately 0.005 to 6% by weight.

The medium (or support) suitable for dyeing generally consists of a mixture of water and at least one organic solvent for dissolving water or compounds which are poorly soluble in water. Examples of organic solvents include, for example, lower alkanols having 1 to 4 carbon atoms, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, and benzyl alcohol or phenoxyethanol. And the like and similar substances and mixtures thereof. The solvent can preferably be present in a proportion of between approximately 1 and 40% by weight, more preferably between 5 and 30% by weight, relative to the total weight of the dye composition.

The pH of the dye composition according to the invention is generally between approximately 3 and 12, preferably between 5 and 11. It can be adjusted to the desired value using acidifying or basifying agents commonly used to dye keratinous fibers, or alternatively using standard buffer systems. Among the acidifying agents, there may be mentioned, for example, inorganic or organic acids such as carboxylic acids, sulfonic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, acetic acid, tartaric acid, citric acid or lactic acid. Among the basifying agents, for example, aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the following formula (II):

[0022]

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[W is a hydroxyl group or C
₁ -C ₄ substituted with an alkyl group be also good propylene residues; the same or different optionally R ₅ also, R _6, R ₇ and R ₈ are hydrogen C ₁ -C ₄ alkyl or C ₁ -C Which represents a ₄ -hydroxyalkyl group].

In addition to the dyes defined above, the dye compositions according to the invention can contain at least one further oxidation base which can be selected from the oxidation bases conventionally used in oxidation dyeing, Among them, in particular, paraphenylenediamine, bis (phenyl) alkylenediamine, paraaminophenol, ortho-aminophenol and the pyrazolo [1,1] of the formula (I) used in the present invention
5-a] Heterocyclic bases other than pyrimidine derivatives.

Among the para-phenylenediamines, more preferably, for example, French Patent Application No. 2,630,43
Para-phenylenediamine, para-toluylenediamine, 2,6-dimethylpara-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-n-propyl-para-phenylenediamine described in No. 8 , 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) -para-phenylenediamine, N, N-bis (β-hydroxyethyl)-
Examples include para-phenylenediamine, 4-amino-N- (β-methoxyethyl) aniline and para-phenylenediamine and its addition salts.

Among the bis (phenyl) alkyldiamines, more preferably, for example, N, N′-bis (β-hydroxyethyl) -N, N′-bis (4′-aminophenyl) -1, 3-diaminopropanol, N,
N′-bis (β-hydroxyethyl) -N, N′-bis (4′-aminophenyl) ethylenediamine, N, N ′
-Bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N,
N'-bis (4-aminophenyl) -tetramethylenediamine, N, N'-bis (4-methylaminophenyl)
-Tetramethylenediamine and N, N'-bis (ethyl) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, and addition salts thereof.

Among the para-aminophenols, more preferably, for example, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol , 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2
-Methoxymethylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-([beta] -hydroxyethylaminomethyl) phenol, and addition salts thereof. Among the ortho-aminophenols, more preferably, for example, 2-aminophenol,
2-amino-5-methylphenol, 2-amino-6
Methyl phenol and 5-acetamido-2-aminophenol and its addition salts are mentioned.

Among the heterocyclic bases, more preferably,
For example, pyrazolo [1,5] of the formula (I) used in the present invention.
-A] Pyridine derivatives other than pyrimidine derivatives, pyrimidine derivatives and pyrazole derivatives, and addition salts thereof. If they are used, these further oxidation bases preferably represent approximately 0.0005 to 12% by weight, more preferably approximately 0.005 to 6% by weight, based on the total weight of the dye composition.

The oxidation dye compositions according to the invention can also contain at least one coupler and / or at least one direct dye, in particular for modifying the shade or for enriching them with brilliance. It is. Couplers that can be used in the oxidation dye composition of the present invention,
Couplers customarily used in oxidation dyeing can be selected among them, in particular, heterocyclic couplers such as meta-phenylenediamine, meta-aminophenol, meta-diphenol and, for example, indole derivatives, and And the addition salts thereof.

More specifically, these couplers are
-Methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,
3-dihydroxy-2-methylbenzene, 4-chloro-
1,3-dihydroxybenzene, 2,4-diamino-1
-(Β-hydroxyethyloxy) benzene, 2-amino-4- (β-hydroxyethyl) amino-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane , 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxyindole and 4-hydroxy-N-methylindole, and addition salts thereof. When present, these couplers are
Preferably, approximately 0.00 relative to the total weight of the dyeing composition.
01 to 10% by weight, more preferably about 0.005
To 5% by weight.

Further, the dyeing composition of the present invention comprises an anionic, cationic, nonionic, zwitterionic or zwitterionic surfactant or a mixture thereof, anionic, cationic, nonionic, zwitterionic or zwitterionic. Ionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, fillers such as silicones, film formers, preservatives and opacifiers It is possible to include various adjuvants conventionally used in compositions for dyeing hair, such as agents. Of course, those skilled in the art will recognize that the advantageous properties inherent in the oxidation dye compositions of the present invention can be such that they are not adversely affected or substantially not affected by the possible additive (s). )
Care will be taken to select any additional compound (s).

The dye compositions of the present invention may be in a variety of forms, such as in the form of a liquid, cream or gel, or any other form suitable for dyeing keratin fibers, especially human hair. The subject of the present invention is also a method for dyeing keratin fibres, in particular human keratin fibres, such as hair, using a dyeing composition as defined above. According to the method of the present invention, at least one dye composition as defined above,
Apply to the fiber in air or with an oxidizing agent for a time sufficient to produce the desired coloration. The dye composition can, if desired, contain an oxidation catalyst to accelerate the oxidation process.

According to a first embodiment of the method of the invention,
The fibers are colored simply by contact with atmospheric oxygen without the addition of an oxidizing agent. According to a second embodiment of the method of the invention, at least one dye composition as defined above is applied to the fiber, the coloring being added to the dye composition only at the time of use, or simultaneously or separately sequentially Oxidation occurs at acidic, neutral or alkaline pH using an oxidizing agent present in the oxidizing composition applied to. According to this second embodiment of the dyeing method of the present invention, the dye composition preferably comprises, in use, an amount of at least one oxidizing agent sufficient to cause coloration in a medium suitable for dyeing. Is mixed with an oxidizing composition containing The resulting mixture is then applied to the keratin fibers and left in place for approximately 3 to 50 minutes, preferably approximately 5 to 30 minutes, after which the fibers are rinsed, washed with shampoo and rinsed again,
dry.

The oxidizing agent present in the oxidizing composition as defined above is selected from oxidizing agents conventionally used for oxidative dyeing of keratin fibers, among which hydrogen peroxide, urea peroxide, alkali bromide are used. Metal salts and persalts such as perboric acid and persulfuric acid. Hydrogen peroxide is particularly preferred. The pH of the oxidizing composition containing an oxidizing agent as defined above,
After mixing with the dye composition, the resulting composition applied to the keratin fibers is preferably in the range of approximately 3 to 12, more preferably 5 to 11. It is adjusted to the desired value with the acidifying or basifying agents defined above, which are usually used for dyeing keratin fibers.

The oxidizing composition as defined above can also contain various adjuvants as defined above, which are conventionally used in compositions for dyeing hair. The composition ultimately applied to the keratin fibers can be in various forms, such as in the form of a liquid, cream or gel or any other form suitable for dyeing keratin fibers, especially human hair It is.

Another subject of the present invention is a multi-compartment staining "kit" or device or other multi-compartment packing system, the first compartment of which contains a dye composition as defined above, and the second of which comprises a second compartment. The compartment contains an oxidizing composition as defined above. French Patent No. 2,586,91 in the name of the applicant
These devices, such as the device described in No. 3, can be provided with means that allow the desired mixture to be applied to the hair. Certain compounds of formula (I) used as oxidation bases in the sense of the present invention are novel and, in that respect, constitute another subject of the present invention. These novel pyrazolo [1,5-a] pyrimidine derivatives,
Addition salts with acids or bases and, if a tautomeric equilibrium exists, its tautomeric form are of the following formula (I ′):

[0037]

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Wherein the groups R ₁ , R ₂ , R ₃ , R ₄ , X, i,
n, p and q have the same meanings as given in formula (I)], except: Pyrazolo [1,5-a] pyrimidine-6,7-diamine; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazolo [1 , 5-a] pyrimidine-3,7-diamine; -2,5-N7, N7-tetramethylpyrazolo [1,
5-a] pyrimidine-3,7-diamine; 2,3-dimethylpyrazolo [1,5-a] pyrimidine-6,7-diamine; 6-amino-5-methylpyrazolo [1,5-a] Pyrimidin-7-ol; 2,5-dimethyl-6-phenyl [1,5-a] pyrimidin-3,7-diamine; 2,6-dimethyl-5-benzyl [1,5-a] pyrimidine- 3,7-diamine; and its addition salts.

Among the novel compounds of the formula (I '), in particular:
The following are mentioned. Pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2-methylpyrazolo [1,5-a] pyrimidine-
3,7-diamine; -2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; -pyrazolo [1,5-a] pyrimidine-3,5-diamine; -2,7 -Dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; -3-aminopyrazolo [1,5-a] pyrimidine-7
-3-amino-5-methylpyrazolo [1,5-a] pyrimidin-7-ol;-3-aminopyrazolo [1,5-a] pyrimidine-5
-Ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; -3-amino-7- [beta] -hydroxyethylamino-5
-Methylpyrazolo [1,5-a] pyrimidine; -2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; -2-[(3-aminopyrazolo [1,5-a] pyrimidine- 7-yl)-(2-hydroxyethyl) amino]
Ethanol;-[2-[(7-aminopyrazolo [1,5-a] pyrimidin-3-yl)-(2-hydroxyethyl) amino]
Ethanol; and its addition salts and tautomers, if any.

The pyrazolo [1,5-a] pyrimidine derivatives of the formula (I) and their salts and tautomeric forms as defined above are used in compositions intended for photographic or chemical imaging and as oxidized bases in their preparation It is also possible. The following examples illustrate the invention but do not limit the scope of the invention.

[0041]

EXAMPLES Example 1: Pyrazolo [1,5-a] pyrimidine-3,7-diamine dihydrochloride First step: 3-Nitropyrazolo [1,5-a] pyrimidin-7-ylamine hydrochloride

[0042]

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50 g of 4-nitro-2H-pyrazole-
3-ylamine hydrochloride (H. Dornand H. Dilcher, Liebi
gs Ann. Chem., 707, 141, 1967), 35 g
Β-ethoxyacrylonitrile and 250 cc of acetic acid were introduced into a 500 cc three-necked round bottom flask equipped with a mechanical stirrer and equipped with a condenser and a thermometer. The medium was refluxed for 4 hours 30 minutes. The mixture was cooled to about 40 ° C., then the precipitate was filtered. The precipitate was taken up in 300 cc of ethyl ether with stirring. The precipitate was filtered again, washed with 100 cc of ethyl ether and the product was dried under vacuum over phosphorus pentoxide. 61.3g of 3
-Nitropyrazolo [1,5-a] pyrimidin-7-ylamine hydrochloride was obtained in the form of a yellow powder (yield = 93).
%). _{NMR (DMSO-d 6):} 6.70 (d; 1H); 8.
34 (d; 1H); 8.99 (s; 1H); 9.56
(S; NH ₂ ); 11.96 (s; NH ⁺ ) Elemental analysis: NW as C6H5N5O2 · HCl
= 215.6

[0044]

[Table 1]

Second step: pyrazolo [1,5-a] pyrimidine-3,7-diamine dihydrochloride

[0046]

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30 g of 3-nitropyrazolo [1,5-
a] Pyrimidin-7-ylamine hydrochloride, 7 g of 10%
Palladium on carbon, 85 g cyclohexene and 60 g
0 cc of acetic acid was introduced into a 1000 cc three-necked round bottom flask equipped with a mechanical stirrer and equipped with a condenser and a thermometer. The medium is refluxed for 4 hours 30 minutes, then
The catalyst was filtered through celite. The catalyst impregnated with the product was taken up in 500 cc of reflux water and filtered again. 2
The filtrates were combined and evaporated. 40 g of a beige powder were obtained. Take this solid in 55cc concentrated hydrochloric acid,
Refluxed for 3 hours. The product was filtered at 15 ° C. and dried under vacuum over phosphorus pentoxide. 25 g of an off-white powder were obtained, and the product was recrystallized from 80 cc of concentrated hydrochloric acid. 18 g of pyrazolo [1,5-a] pyrimidine-3,
7-Diamine dihydrochloride was obtained as a white powder (yield = 60%). _{NMR (DMSO-d 6):} 6.45 (d; 1H); 8.
36 (d; 1H); 8.39 (s; 1H); 8.60-1
1.50 (6H) Elemental _{analysis: C 6 H 7 N 5 ·} 2HCl · 0.5H 2 O as NW = 231

[0048]

[Table 2]

Example 2: 3-aminopyrazolo [1,5-
a] Pyrimidin-7-ol hydrochloride First step: 3-nitropyrazolo [1,5-a] pyrimidin-7-ol

[0050]

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2 g of 4-nitro-2H-pyrazole-3
-Ylamine hydrochloride (H. Dornand H. Dilcher, Liebigs
Ann. Chem., 707, 141, 1967), 1.55
g of methyl 3-methoxyacrylate and 20 cc of absolute ethanol were introduced into a 50 cc three-necked round bottom flask equipped with a mechanical stirrer and equipped with a condenser and a thermometer. The medium was refluxed for 5 hours, then the precipitate was filtered while hot. 1.2 g of a yellow solid were obtained. Silica gel (Merck: 230-400 mesh; EtOAc /
MeOH = 9: 1), 0.4 g of 3-nitropyrazolo [1,5-a] pyrimidin-7-ol were obtained in the form of a yellow powder. (Yield = 18%) NMR (DMSO- d 6): 6.19 (d; 1H); 7.
98 (d; 1H); 8.75 (s; 1H); 13.10
(OH)

Second step: 3-aminopyrazolo [1,5-
a] Pyrimidin-7-ol hydrochloride

[0053]

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0.35 g of 3-nitropyrazolo [1,5
-A] pyrimidin-7-ol, 20 cc acetic acid, 1.
6 g of cyclohexene and 85 mg of 10% palladium on carbon were introduced into a 50 cc three-neck round bottom flask equipped with a mechanical stirrer and equipped with a condenser and a thermometer. The medium was refluxed for 1 hour 30 minutes and then the catalyst was filtered through celite. After evaporation of the acetic acid, the resulting solid was taken up in 2 cc of 2 cc of refluxing concentrated hydrochloric acid for 2 hours 30 minutes. After evaporation of the solvent, an off-white solid was collected. _{NMR (D 2 O): 5.93} (d; 1H); 7.87 (d
; 1H); 8.04 (s; 1H)

Example 3 3-Amino-5-methylpyrazolo [1,5-a] pyrimidin-7-ol hydrochloride First step: 3-nitro-5-methylpyrazolo [1,5-
a] Pyrimidin-7-ol

[0056]

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50 g of 4-nitro-2H-pyrazol-3-ylamine hydrochloride (H. Dorn in 160 cc of acetic acid)
and H. Dilcher, Liebigs Ann. Chem., 707, 141, 1967.
And 60 g of ethyl acetoacetate were mixed with 500 g equipped with a mechanical stirrer, condenser and thermometer.
cc into a three neck round bottom flask. 12 reaction media
Refluxed for hours. The precipitate formed was filtered at about 90 ° C.
It was rinsed with diisopropyl ether and dried under vacuum over phosphorus pentoxide. 50 g of 3-nitro-5-methylpyrazolo [1,5-a] pyrimidin-7-ol were obtained in the form of yellow crystals. (Yield = 84.5%; mp = 290 ° C. _{decomposition) NMR (DMSO-d 6)} : 2.42 (s; 3H); 6.
03 (s; 1H); 8.61 (d, 1H); 12.69
(S, 1H) Elemental Analysis: NW as _{C 7 H 6 N 4 O 3} = 194.15

[0058]

[Table 3]

Second step: 3-amino-5-methylpyrazolo [1,5-a] pyrimidin-7-ol hydrochloride

[0060]

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150 cc of acetic acid and 150 cc of water are introduced into a 1 liter autoclave, followed by 1 g of 10 g of 3-nitro-5-methylpyrazolo [1,5-a] pyrimidin-7-ol and 50% water. 5% palladium on carbon (Engelhard) was introduced. 5 bar of hydrogen were introduced into the reactor and preheated at 30 ° C. After reacting for 1 hour, the catalyst was filtered through celite. 1 filtrate
Acidified with 00 cc of 7M hydrochloric acid solution. The hydrochloride was precipitated with stirring. It was filtered and washed with diisopropyl ether. 4.2 g of 3-amino-5-methylpyrazolo [1,5-a] pyrimidin-7-ol hydrochloride were obtained in the form of white crystals. (Yield = 41%) NMR (DMSO- d 6): 2.37 (s, 3H); 5.
71 (s, 1H); 8.00 (s, 1H); 10.32.
(Broad s, 3H); 13.09 (broad s, 1
H) Elemental analysis: NW = 2 as _{C 7 H 8 N 4 O ·} HCl
0.003

[0062]

[Table 4]

Example 4: 3-amino-7-βhydroxyethylamino-5-methylpyrazolo [1,5-a] pyrimidine dihydrochloride First step: 7-chloro-5-methyl-3-nitropyrazolo [1, 5-a] pyrimidine

[0064]

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230 cc of phosphorus oxychloride, 15.4 g
N, N-dimethylaniline and 23.3 g of 3-amino-5-methylpyrazolo [1,5-a] pyrimidine-
The 7-ol was introduced into a 500 cc three-necked round bottom flask equipped with a mechanical stirrer, condenser and thermometer. The reaction medium was refluxed for 2 hours 30 minutes. After evaporation of the phosphorus oxychloride under reduced pressure, a very viscous green oil was obtained, to which was added about 400 g of ice. A brown solid precipitated. After stirring for 30 minutes, the precipitate was filtered, rinsed with petroleum ether, and then rinsed with diisopropyl ether. After drying under vacuum over phosphorus pentoxide, 21.4 g
Of 7-chloro-5-methyl-3-nitropyrazolo [1,
5-a] Pyrimidine was obtained in the form of a brown solid. (Yield = 83.9%). _{NMR (DMSO-d 6):} 2.70 (s, 3H); 7.
82 (s, 1H); 9.10 (s, 1H)

Second step: 7-β-hydroxyethylamino-5-methyl-3-nitropyrazolo [1,5-a]
Pyrimidine

[0067]

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15 g of 7- in 100 cc of ethanol
Chloro-5-methyl-3-nitropyrazolo [1,5-
a] Pyrimidine was introduced into a 250 cc three-necked round bottom flask equipped with a mechanical stirrer, condenser and thermometer. 5 g of ethanolamine were added dropwise and the medium was refluxed for 30 minutes. After cooling to room temperature, the yellow precipitate was filtered. The precipitate was rinsed with diisopropyl ether. After drying under vacuum over phosphorus pentoxide, 14.2 g of 7-β-
Hydroxyethylamino-5-methyl-3-nitropyrazolo [1,5-a] pyrimidine was obtained in the form of yellow crystals. (Yield = 86%, melting point = 231 ° C). _{NMR (DMSO-d 6):} 2.52 (s, 3H); 3.
52 (m, 2H); 3.66 (m, 2H); 4.96
(T, 1H); 6.64 (s, 1H), 8.48 (t, 1H)
H); 8.89 (s, 1H) Elemental analysis: C ₉ H ₁₁ N ₅ O ₃ MW = 237.22

[0069]

[Table 5]

Third step: 3-amino-7-β-hydroxyethylamino-5-methylpyrazolo [1,5-a]
Pyrimidine dihydrochloride

[0071]

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14 g of 7-β-hydroxyethylamino-5-methyl-3-nitropyrazolo [1,5-a] pyrimidine in 150 cc of acetic acid and 150 cc of water was added to 50
A 0 cc autoclave was introduced, followed by 1 g of 5% palladium on carbon (Engelhard) containing 50% water. The reaction medium was preheated to 30 ° C. and hydrogen at a pressure of 8-bar was introduced. The reaction started immediately and the temperature reached 60 ° C. At the end of the reaction, the catalyst was filtered through Celite. The filtrate was acidified with a 7M hydrochloric acid solution. The hydrochloride was precipitated with stirring. It was filtered and washed with diisopropyl ether. 10 g of 3-amino-7-β-hydroxyethylamino-5-methylpyrazolo [1,5-a] pyrimidine dihydrochloride were obtained in the form of slightly gray crystals. (Yield _{= 60%) NMR (D 2} O): 2.73 (s, 3H); 3.91
(M, 2H); 3.98 (m, 2H); 6.66 (s, 1
H); 8.39 (s, 1H ) Elemental _{analysis: C 9 H 13 N 5 O} · 2HCl NW = 280.
16

[0073]

[Table 6]

Example 5 2-methylpyrazolo [1,5-
a] Pyrimidine-3,7-diamine dihydrochloride First step: 2-methylpyrazolo [1,5-a] pyrimidin-7-ylamine hydrochloride

[0075]

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150 cc of 35% hydrochloric acid was added to a mechanical stirrer,
The mixture was introduced into a 500 cc three-neck round bottom flask equipped with a thermometer and a condenser, and 7.5 g of 3-amino-5-methylpyrazole dissolved in 100 cc of water was added dropwise. The temperature rose to 60 ° C. Then 47.5 g of 3-ethoxyacrylonitrile was added and the reaction was refluxed for 1 hour. The reaction medium was cooled and concentrated under reduced pressure. 50
cc of acetone was added and the resulting precipitate was filtered. It was rinsed with diisopropyl ether. After drying under vacuum over phosphorus pentoxide, 78.7 g of 2-methylpyrazolo [1,5-a] pyrimidin-7-ylamine hydrochloride were obtained in the form of white crystals. (Yield = 83%) NMR (DMSO- d 6): 2.43 (s, 3H); 6.
42 (s, 1H); 6.46 (d, 1H); 8.26
(D, 1H); 9.55 (broad s, 1H); 10.3
2 (broad s, 1H) Elemental _{analysis: C 7 H 8 N 4 ·} HCl · 0.5H 2 O NW =
193.63

[0077]

[Table 7]

Second step: 2-methyl-3-nitropyrazolo [1,5-a] pyrimidin-7-ylamine

[0079]

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27 cc of 98% sulfuric acid are introduced into a 100 cc three-necked round bottom flask equipped with a mechanical stirrer, thermometer and condenser, after which 5.5 g of 2-methylpyrazolo [1,5-a] are obtained. Pyrimidin-7-ylamine hydrochloride was dissolved little by little at 5 ° C. Then 1.9
A mixture of 8 g of fuming nitric acid and 5 cc of 98% sulfuric acid was added to 3
It was added dropwise over 0 minutes. After 2 hours 30 minutes of reaction, the medium is poured into 200 cc of ice-cold water and 122 g of 20%
Neutralized with aqueous ammonia. The green precipitate formed was filtered. After drying under vacuum over phosphorus pentoxide, 3.8 g of 2-methyl-3-nitropyrazolo [1,5-a] pyrimidin-7-ylamine were obtained in the form of a green powder.
(Yield = 66%) NMR (DMSO- d 6): 2.62 (s, 3H); 6.
39 (s, 1H); 8.24 (s, 1H); 8.39 (broad s, 2H)

Third step: 2-methylpyrazolo [1,5-
a] Pyrimidine-3,7-diamine dihydrochloride

[0082]

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3.9 g of 2 in 150 cc of methanol
-Methyl-3-nitropyrazolo [1,5-a] pyrimidin-7-ylamine was introduced into a 250 cc reactor, followed by 5% palladium on carbon containing 50% water (Engel
hard) was introduced. 10-bar pressure of hydrogen was introduced into the reactor and the medium was brought to 90 ° C. After reaction for 40 minutes, the catalyst was filtered through celite and a stream of hydrogen chloride gas was passed through the filtrate. After stirring for 1 hour, the precipitate was filtered. It was washed with diisopropyl ether and dried under vacuum over phosphorus pentoxide. 2.2 g of 2-methylpyrazolo [1,5-a] pyrimidine-3,7-diamine dihydrochloride were obtained in the form of gray crystals. (Yield = 46.5%) NMR (DMSO- d 6): 2.60 (s, 3H); 6.
50 (d, 1H); 8.45 (d, 1H); 9.98 ( broad s, 2H); 10.88 (broad s, 4H) Elemental _{analysis: C 7 H 9 N 5 ·} 2HCl NW = 236. 1

[0084]

[Table 8]

Application Examples Dyeing in alkaline medium Examples 1 to 9 The following dye compositions according to the invention were prepared (content in grams):

[0086]

[Table 9]

(*) Common Dye Support 1: -96 g ethanol 9.0 g-diethylenetriaminopentaacetic acid pentasodium salt 0.54 g-35% sodium metabisulfite 0.29 g-20% ammonia water 5.0 g- Demineralized water total 50g

At the time of use, each dye composition 1 to 9 was mixed with 50 g of a 20-volume hydrogen peroxide solution (6% by weight) whose pH was adjusted to approximately 2.5 with orthophosphoric acid. Each of the resulting compositions was applied at a rate of 10 g / g of hair to natural gray hair containing 90% gray hair, or a bundle of permanently wavy hair immediately for 30 minutes. The tress was then rinsed, washed with a standard shampoo, and then dried. The tresses were dyed in the shades shown in the table below.

[0089]

[Table 10]

Dyeing Examples 10 to 18 in Acidic Media The following dye compositions of the invention were prepared (content in grams):

[0091]

[Table 11]

(**) Common dye support 2: -9.0 g of 96-ethanol-0.54 g of diethylenetriaminopentaacetic acid pentasodium salt-0.29 g of 35% sodium metabisulfite-K ₂ HPO ₄ / KH ₂ PO ₄ (1.5M / 0.5M) 5.0g-Demineralized water Total 50g

The pH of each of the dye compositions 10 to 18 was adjusted to about 2.5 with orthophosphoric acid at the time of use.
0 g of a 20-volume hydrogen peroxide solution (6% by weight) was mixed. Each of the resulting compositions is weighed at 10 g / g of hair
At a rate of 3% on natural gray hair containing 90% gray hair or on a bundle of permanent wavy hair immediately
Applied for 0 minutes. The tress was then rinsed, washed with a standard shampoo, and then dried. The tresses were dyed in the shades shown in the table below.

[0094]

[Table 12]

Dyeing Examples in Alkaline Media Examples 19 to 21 The following dye compositions of the invention were prepared (content in grams):

[0096]

[Table 13]

(*) Common dye support 1: This is the same as that used in Examples 1 to 9. The dye was then prepared according to the processes described in Examples 1-9 above. The tresses were dyed in the shades shown in the table below.

[0098]

[Table 14]

Dyeing Examples 22 to 24 in Acidic Media The following dye compositions of the invention were prepared (content in grams):

[0100]

[Table 15]

(**) Common dye support 2: This is the same as that used in Examples 10 to 18. Dyes were then prepared according to the processes described in Examples 10-18 above. The tresses were dyed in the shades shown in the table below.

[0102]

[Table 16]

Comparative Examples 25 to 32 The following dye compositions were prepared according to the invention (content in grams):

[0104]

[Table 17]

(*) Common dye support 1: This is the same as that used in Examples 1 to 9. (***): Example not forming part of the present invention

Next, a dyeing operation was performed on a bundle of natural gray hair containing 90% gray hair according to the process described in Examples 1 to 9 above. Then, change the color of the bundle to Minolta CM
Evaluation was performed in a Munsell system using a 2002 colorimeter. The dyed swatches were then subjected to a test for shampoo resistance (automatic machine). To do this, a bundle of hair was placed in a cup, which was dipped in a standard shampoo solution at 37 ° C.
The basket was subjected to variable frequency up and down and rotating movements, which simulated hand rubbing, thereby causing foam to form.

After the 3 minute test, the bundles were removed, rinsed and then dried. The dried bundle was subjected to six consecutive shampoo tests. The bundle color was then re-evaluated in the Munsell system using a Minolta CM 2002 colorimeter to determine the color loss after these six shampoo washes. Muns
According to ell's note, color is defined by the expression HV / C, where the three parameters indicate hue or hue (H), intensity or value (V) and purity or chromaticity (C), respectively. The diagonal lines in this expression are simple promises and do not indicate a ratio.

The color difference between the two bundles is, for example, “Co
uleur, Industrie et Technique ", pp. 14-17; vol.
No. 5; Nickerson equation described in 1978: ΔE =
Calculated by applying 0.4CoΔH + 6ΔV + 3ΔC. In this equation, ΔE represents the color difference between the two bundles, ΔH, ΔV and ΔC represent the changes in the absolute values of the parameters H, V and C, and Co represents the bundle for which it is desired to evaluate the color difference. Represents the purity of The results are shown in the table below.

[0109]

[Table 18]

(***) Example not forming part of the present invention

The results are shown in Examples 25 and 2 of the present invention.
The compositions of 7, 29 and 31, ie containing pyrazolo [1,5-a] pyrimidine-3,7-diamine dihydrochloride as the oxidation base, do not form Examples 26, 28, 30 And 32 compositions, ie,
For example, 4,5,6,7-tetrahydropyrazolo [1,5- described in German Patent Application No. 4,133,957.
a] indicates that it leads to a shampoo-resistant color which is considerably better than that containing pyrimidin-3-ylamine trihydrochloride as oxidized base.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Alain Lagrange France 77450 Cuvray Rue de Montry 5

Claims (2)

[Claims] 1. The formula: embedded image[Wherein, R which may be the same or different₁, R_Two, R_ThreeAnd R_Four
Is a hydrogen atom, C₁-C_FourAlkyl group, aryl group, C₁−
C_FourHydroxyalkyl group, C_Two-C_FourPolyhydroxya
Alkyl group, (C₁-C_Four) Alkoxy (C₁-C_Four) Archi
Group, C₁-C_FourAn aminoalkyl group (the amine is acetyl
Or ureido or sulfonyl),
(C₁-C_Four) Alkylamino (C₁-C_Four) Alkyl groups,
Di [(C₁-C_Four) Alkyl] amino (C₁-C_Four) Archi
(The dialkyl is a 5- or 6-membered alicyclic or
Capable of forming a heterocyclic ring) or hydroxy (C
₁-C_Four) Alkylamino (C₁-C_Four) Alkyl group or
Di [hydroxy (C₁-C_Four) Alkyl] amino (C₁−
C_Four) Represents an alkyl group;-may be the same or different
Group X is a hydrogen atom, C₁-C_FourAlkyl group, aryl group,
C₁-C_FourHydroxyalkyl group, C_Two-C_FourPolyhydroxy
Silalkyl group, C ₁-C_FourAn aminoalkyl group, (C₁−
C_Four) Alkylamino (C₁-C_Four) Alkyl groups, di
[(C₁-C_Four) Alkyl] amino (C₁-C_Four) Alkyl
A group wherein the dialkyl is a 5- or 6-membered cycloaliphatic or
A cyclic ring), hydroxy (C₁-C_Four)
Alkylamino (C₁-C_Four) Alkyl group, di [hydroxy
Shi (C₁-C_Four) Alkyl] amino (C₁-C_Four) Alkyl
Group, amino group, (C₁-C_Four) Alkylamino group or di
[(C₁-C_Four) Alkyl] amino group, halogen atom,
I represents 0, 1, 2 or 3; -p equals 0 or 1; -q equals 0 or 1; -n equals 0 or 1; Where: (i) the sum of p + q is not 0; and (ii) if p + q is equal to 2, then n is equal to 0.
NR₁R_TwoAnd NR_ThreeR_FourIs position (2,3);
(5,6); (6,7); (3,5) or (3,7)
(Iii) if p + q is equal to 1, then n is equal to 1
Shiki, group NR₁R_Two(Or NR_ThreeR_Four) And the OH group
(2,3); (5,6); (6,7); (3,5)
Or (3,7), with the proviso that:-pyrazolo [1,5-a] pyrimidine-6,7-dia
Min; -5,6-dimethylpyrazolo [1,5-a] pyrimidi
-3,7-diamine; -2,6-dimethylpyrazolo [1,5-a] pyrimidi
-3,7-diamine; -2,5-N7, N7-tetramethylpyrazolo [1,
5-a] pyrimidine-3,7-diamine; -2,3-dimethylpyrazolo [1,5-a] pyrimidi
-6,7-diamine; 6-amino-5-methylpyrazolo [1,5-a] pi
-Limidin-7-ol; -2,5-dimethyl-6-phenyl [1,5-a] pi
Limidine-3,7-diamine; -2,6-dimethyl-5-benzyl [1,5-a] pi
Limidine-3,7-diamine; and its addition salts
Pyrazolo [1,5-a] pyrimidine derivatives, acid
Or addition salts with bases and tautomeric equilibrium exist
Is its tautomer. 2. Pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2-methylpyrazolo [1,5-a] pyrimidine-
3,7-diamine; -2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; -pyrazolo [1,5-a] pyrimidine-3,5-diamine; -2,7 -Dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; -3-aminopyrazolo [1,5-a] pyrimidine-7
-3-amino-5-methylpyrazolo [1,5-a] pyrimidin-7-ol;-3-aminopyrazolo [1,5-a] pyrimidine-5
-Ol; 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; -3-amino-7- [beta] -hydroxyethylamino-5
-Methylpyrazolo [1,5-a] pyrimidine; -2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; -2-[(3-aminopyrazolo [1,5-a] pyrimidine- 7-yl)-(2-hydroxyethyl) amino]
Ethanol;-[2-[(7-aminopyrazolo [1,5-a] pyrimidin-3-yl)-(2-hydroxyethyl) amino]
2. Ethanol; and its addition salts and, where a tautomeric equilibrium is present, selected from its tautomers.
The derivative according to 1.